Chrysanthemic acid esters and their use as insecticides

ABSTRACT

WHEREIN R1 - R7 is hydrogen or an alkyl group. The compounds of formula I are useful as insecticides and are prepared by reacting an acid chloride with alcohol or by reacting a halide with a salt of a chrysanthemum carboxylic acid.   WHEREIN Y is the moiety   The invention comprises chrysanthemic acid ester compounds of the formula

llnited States atet Osbond et al.

1111 3,869,552 Mar. 4, r975 CHRYSANTHEMIC ACID ESTERS AND THEIR USE ASINSECTICIDES [75] Inventors: John Mervyn Osbond, Hatfield;

James Charles Wickens, Saint Albans, both of England [73] Assignee:Hoffmann-La Roche Inc., Nutley,

[221 Filed: Feb.ll, 1972 [21] Appl.No.:225,597

Related U.S. Application Data [62] Division of Ser. No. 880.964, Nov. 281969, Pat. No.

[30] Foreign Application Priority Data Primary Eraminer-Vincent D.Turner Attorney, Agent, or Firm-Samuel L. Welt; Jon S. Saxe; William H.Epstein ABSTRACT The invention comprises chrysanthemic acid estercompounds of the formula wherein Y is the moiety n Rx m) wherein R R, ishydrogen or an alkyl group. The compounds of formula I are useful asinsecticides and are prepared by reacting an acid chloride with alcoholor by reacting a halide with a salt of a chrysanthemum carboxylic acid.

3 Claims, No Drawings CHRYSANTI-IEMIC ACID ESTERS AND THEIR USE ASINSECTICIDES This is a division of application Ser. No. 880,964 filedNov. 28, 1969, now US. Patent 3,663,591.

This invention relates to the esters of formula I which are useful asinsecticides. These esters can be incorporated into insecticidalcompositions which contain as an active ingredient a chrysanthemic acidester and a compatible carrier material.

The unique compounds of the present invention are represented by theformula wherein Y is a moiety selected from the group conwherein R R R RR R and R is each independently selected from the group consisting of ahydrogen atom and lower alkyl,at least one of R, R and R is other thanhydrogen.

Although the chrysanthemic acid esters produced in accordance with thisinvention are particularly useful in combating Musca domestica, thecompounds are also useful in that they exhibit significant insecticidalactivity against bean aphids, red spider mite, codling moth and Coloradobeetle while evidencing a relatively low mammalian toxicity. In fact,the significant insecticidal activity of the compounds of Formula I issurprising especially since Elliott et al. (Nature, 207, 938, [1965])reported a related, but dissimilar ester to be non-toxic to undesirableinsects such as mustard beetles and Musca domcsticu.

In accordance with custom and usage in the art, the third bond,optionally present in the structure of the moiety of formula (d), isdepicted by a broken line. Likewise, it will be understood that the termlower alkyl comprehends the use of both straight-chain andbranched-chain alkyl groups containing anywhere from one to seven carbonatoms, e.g. methyl, ethyl, isopropyl and the like. In a preferredembodiment the lower alkyl group will represent a methyl group.

The chrysanthemic acid esters illustrated in formula I comprise severalclasses of compounds. For example, the symbol Y can represent the moietyof formula (21). in which case the esters would have the formula whereinR, R and R are of the same meaning as above defined, at least one of .R,R and R is other than hydrogen. Esters illustrative of this class are:5-methyl-5-hexen-2- ynyl (i)cis/trans-2,2-dimethyl-3-(Z-methylpropenylycyclopropane carboxylate; and5,6-dimethyl-5-hepten-Z-ynyl (:)-cis/trans2,2-dimethyl-3-(Z-methyl-propenyl)-cyclopropane car-boxylate.

A second class of chrysanthemic acid esters of formula l is thecompounds in which Y is the moiety of formula (b). In this instance, theesters would be represented by the formula wherein R R and R eachindividually represent a hydrogen atom or a lower alkyl group.Preferably R R and R, will each represent a hydrogen atom or in anotherpreferred embodiment of this class, one of the three symbols willrepresent a lower alkyl while the remaining two symbols each represent ahydrogen atom. Esters exemplary of this class are: cis-2,5- hexadienyl(:t)-cis/trans-2,2-dimethyl-3-(2-methyl' propenyl)-cyclopropanecarboxylate; trans-2,5 hexadienyl(i)-cis/trans-2,2-dimethyl3-(Z-methylpropenyl)-cyclopropane carboxylate;2trans-2,5- heptadienyl(i)-cis/trans-2,Z-dimethyl-3-(2-methylpropenylJ-cyclopropanecarboxylate; and trans-5-methyl-2,5-hexadienyl (i)-cis/trans-2,2dimethyl-3-(Z-methyl-propenyl)-cyclopropane carboxylate.

In another class of compounds, Y can represent the aromatic containingmoiety of formula (c) wherein the esters would be represented by theformula Illustrative of this class is, for example, the ester 2,5-hexadiynyl (i)-cis/trans-2,2-dimethyl-3-( 2-methylpropenyl)-cyclopropanecarboxylate.

Furthermore, Y can represent the moiety of formula (d) in which instancethe esters would be a class of the formula wherein R is a hydrogen atomor a lower alkyl group. Where R represents a hydrogen atom, the esterswithin the class will include, for example, the compounds:4-phenyl-2-butynyl (i)-cis/trans-2,2-dimethyl-3-(Z-methyl-propenyl)-cyclopropane carboxylate andtrans-4-phenyl-2-butenyl (i)-cis/trans-2,2-dimethyl-3-(2-methyl-propenyl)- cyclopropane carboxylate.If, however, R were represented by a lower alkyl, and in particular by apreferred methyl group, an illustrative compound would be4-(Z-methyl-phenyl)-2-butynyl (i)-cis/trans-2,2-dimethyl-3-(2-methyl-propenyl)- cyclopropane carboxylate.

The chrysanthemic acid esters of formula I can be prepared employingeither one of two methods. Firstly, the esters can be produced byreacting an acid chloride of the formula wherein R, R R;,, R,,, R R, andR are as above described.

The reaction of an acid chloride starting material of formula II with analcohol starting material is conveniently carried out in the presence ofan acid-binding agents. Suitable acid-binding agents include alkalimetalcarbonates, alkali-metal bicarbonates, tertiary amines and the like. Forexample, the acid-binding agent can be sodium carbonate, sodiumbicarbonate or triethyl amine; preferably, pyridine is utilized.

In a preferred embodiment, the reaction is carried out in a reactioninert medium such as inert solvent or inert gas. Where the reactionproceeds in the presence of an inert solvent, the inert aolution can bea hydrocarbon (e.g. benzene, toluene, xylene etc.), a haloge natedhydrocarbon (e.g. methylene chloride, chloroform, chlorobenzene etc.),ether (e.g. diethyl etc.) or the like. Furthermore, the reaction can besuitably carried out at a temperature range of from about 0 to about30C. Preferably, however, the reaction is carried out at a temperatureof about 20C in the presence of an inert gas such as nitrogen or argon.

The acid chloride starting materials of formula II are known and havealready been described in the literature. For example, these materialscan be prepared by chlorinating the corresponding carboxylic acid usingthionyl chloride or the like.

The alcohol starting materials of formula Illa llld can be produced by avariety of methods. For example, the alcohols of formula IIIa can beprepared by the method which comprises the reaction of propargyl alcohol with an alkyl-magnesium halide like ethyl magnesium bromide toform a Grignard complex, treating the Grignard complex with cuprouschloride or cuprous cyanide, treating the mixture with a halide of theformula wherein R, R and R are as above defined and O is a chlorine orbromine atom, and decomposing the resultant product by conventionaltechniques such as by treatment with aqueous ammonium chloride.

Alternatively, the alcohols of formula Illa can be prepared bysimultaneously reacting a mixture of propargyl alcohol, cuprous chlorideand sodium chloride in water with sodium hydroxide and a halide offormula Va. ln this regard, see Ann. Chem. 658; 6-20, 1962. The alcoholof formula llla can also be prepared by treating a mixture of propargylalcohol, cuprous chloride and sodium carbonate in acetone with a halideof formula Va. See Bull. Soc. Chim. France, 1957; 1966.

Preparation of the alcohol starting materials of formula lllb can beprepared by reducing an acetylenic alcohol of formula llla (or acorresponding acetylenic alcohol) wherein R R and R each represent ahydrogen atom, or R, represents a hydrogen atom and either R or Rrepresent a hydrogen atom and the other symbol represents a lower-alkylgroup either (1) with an alkali-metal aluminum hydride or (2) withhydrogen in the presence of a partially deactivated palladium catalyst.This reduction with an alkali-metal aluminum hydride such as lithiumaluminum hydride yields an alcohol starting material of formula lllbhaving a trans configuration at the 2,3-position. The reaction isconveniently carried out in an inert organic solvent like diethyl etherat an elevated temperature such as the reflux temperature of thereduction mixture. In contrast, reducing an alcohol of formula llla inthe presence of a partially deactivated palladium catalyst yields analcohol starting material of formula lllb whose configuration is cis atthe 2,3-position.

Deactivation of a palladium catalyst (e.g. LlN- DLAR) can beeffectedaccording to known techniques using lead and quinoline in thepresence of an inert or ganic solvent like petroleum ether.

The acetylenic alcohol starting materials of formula llle and llld canbe prepared in similar manner to that employed for the preparation ofthe alcohols of formula llla. i.e., reacting propargyl alcohol with aGrignard reagent followed by treatment with a halide of the formulawherein Q and R are as above defined,

and decomposition of the resultant product by conventional techniquessuch as treatment with aqueous ammonium chloride.

Alternately, the acetylenic alcohols of formula llld can be prepared byreacting the corresponding arylmagnesium halide (e.g. phenyl-magnesiumbromide) with 4-chloro'2-butyn-l-ol and decomposing the product byconventional techniques such as by treatment with aqueous ammoniumchloride.

Olefinic alcohol starting materials of formula llld can be prepared in amanner similar to that employed in preparing the alcohols of formulallle, i.e., by reducing a corresponding acetylenic alcohol startingmaterial either l with an alkali-metal aluminium hydride or (2) withhydrogen in the presence ofa partially deactivated palladium catalyst.Where the reduction of the acetylenic alcohol is effected using analkali-metal aluminium hydride (e.g. lithium aluminium hydride), theresultant product is an olefinic alcohol starting material 6 of formulallld having a trans configuration at the 2,3- position. This reactionmay be carried out in an inert organic solvent at the reflux temperatureof the reduction mixture.

in contrast, if the alcohol reduction procedure uses hydrogen in thepresence of a partially deactivated palladium catalyst, the alcohol soproduced is an olefin of formula llld, which has a cis configuration atthe 2,3- position.

The second procedure for preparing chrysanthemic acid esters of formula]comprises reacting an alkalimetal salt or a tri(lower alkyl) amine saltofa Chrysanthemum carboxylic acid with a halide of the formula wherein Xis a halogen atom and R, R R R R R and R are as above defined.

The alkali-metal and tri(lower alkyl) amine salts used in this processare prepared by reacting a chrysanthe mum carboxylic acid with analkali-metal hydroxide solution or a tri(lower alkyl) amine in an inertreaction solvent like ethanol. The preferred salts of the alkalimetalsare sodium and potassium and those of the tri(- lower alkyl) amines aretriethyl amine.

Preparation of the halide starting materials of form nlas lVa, IVb, lVcand lVd is by treating an alcohol of formula llla, lllb, [lie or llldwith a halogenating agent (e.g. thionyl chloride, phosphorus tribrotnidein pyridine or sodium iodide in acetone). In a preferred embodiment, thehalides are chlorides or bromides.

Suitably, the reaction of an alkali-metal salt or a tri- (lower alkyl)amine salt of a Chrysanthemum carboxylic acid with a halide of formulalVa, lVb. lVc or lVd is carried out in an inert organic reactionsolvent. however, a ketone such as acetone or methyl ethyl ketone ordiglyme is preferred. Furthermore, in a preferred embodiment thereaction proceeds at an elevated temperature of the reaction mixture andunder the atmo sphere of an inert gas such as nitrogen, argon or thelike.

Since the chrysanthemic acid moiety of formula I exhibits both geometricand optical isomerism and since the alcohol moiety can also exhibitgeometric isomerism whenever a double bond is present in the 2.3-position, it will be appreciated that the esters of the presentinvention encompass not only all of the gco' metric and optical isomers,but also the mixtures thereof too. It should also be appreciated thegeometric isomerism can exist where, for example. Y represents a moietyof formula (a) or (b).

If the salt of Chrysanthemum carboxylic acid and the halide of formulalVa, lVb, lVc or IVd, used in the second described process, are variedthe resultant product will vary. Thus using a mixture of the halide orsalt starting materials can produce a cis/trans mixture.

As noted, the esters of formula I are insecticidally active against avariety of insects. These esters are also insecticidally effective whenthey are synergized with known pyrethrin synergists such as piperonylbutoxide; (l,2-methylene-dioxy)-4-[2-(octylsulfonyl)-propyl]- benzene,bis-(2,3,3,3-tetrachloro-propyl)-ether and the like.

The acid esters of formula I evidencing a relatively low mammaliantoxicity; e.g., 4-phenyl-2-butynyl(i)-cis/trans-2,2-dimethyl-3-(2-methyl'propenyl)- cyclopropane carboxylate;S-methyl-S-hexen-Z-ynyl (i)-cis/trans-2,2-dimethyl-3-(2-methylpropenyl)-cyclopropane carboxylate; 6-methyl-5-hepten-2-ynyl (i)cis/trans-2,2-dimethyl-3-(Z-methyl-propenyl)- cyclopropane carboxylate;and 2,5-hexadiynyl (i)- cis/trans-Z,2-dimethyl-3-(2-methyl-propenyl)-cyclopropane carboxylate-all having a LD greater than 1600 mg/kg p.o. inmice and exhibiting insecticidal activity against Musca domestica in theorder of pyrethrin extract and DDT.

For practical use of the chrysanthemic acid esters of formula l asinsecticides, it is desirable to formulate them as insecticidalcompositions comprising, as an active ingredient, an ester and acarrier. Such formulations can be in liquid form (e.g. as a sprayablesolution or suspension) or in solid form (e.g. as a dust or a granularformulation), either of which includes therewith an acceptable carrier.As used herein, the term acceptable carrier comprehends any substancewhich can be used to dissolve, disperse or diffuse the ester of formula1 without impairing the effectiveness of the toxic agent and which doesnot permanently damage the environment in which it is used, e.g. soilequipment, crops, etc. For example, liquid compositions can be extendedwith water, and dusts and granular formulations can be extended withinert solid carriers. Where a solid carrier is employed in preparing theinsecticidal compositions, such compositions may include talc, finelyparticled clay, silica or similar powders so long as the solid carriersdo not bring about decomposition of the esters. Where, for conveniencethe esters of formula I are formulated as liquid compositions, suchcompositions can include emulsifiers and/or acceptable organic solvnts.If desired, the insecticidal compositions can also contain conventionaladditives such as wetting agents or the like, as well as otherinsecticides and/or synergists.

An effective amount of the insecticidal composition can be applied to aninsect infested area using any conventionally acceptable method such aspraying, dusting, fumigation etc. Desirably, solid formulations andliquid formulations contain from about 0.5 to about 25% by weight of thetoxicant comprising a'chrysanthemic acid ester of formula 1. Solid andliquid formulations preferably contain from about 1% to about 10% on thesame basis. The choice of the concentration of the ester of formula Iand the rate of application to the insect infested area depend of courseon several factors, for example maturity of insects present, the type ofinsecticidal composition used and method of application.

Of course, the insecticidal compositions of this invention may also beconcentrates (e.g. wettable powders or emulsion concentrates) suitablefor storage or transport and containing, for example, from about 10% toabout by weight of a chrysanthemic acid ester of formula I. These can bediluted with the same or a different carrier to a concentration suitablefor application. Emulsion concentrate formulations, for example, can beprepared by dissolving the esters of formula I in an acceptable organicsolvent and adding a solventsoluble emulsifier. Suitable organicsolvents, which are usually water-immiscible, can, for example, be foundin the hydrocarbon, chlorinated hydrocarbon, ketone, ester, alcohol andamide classes of organic solvents, and include toluene, xylene,naphthas, perchloroethylene and the like or mixtures thereof;preferably, the solvents are in the aromatic hydrocarbon and ketoneclasses. Surfactants are useful as emulsifiers and, where used, theysuitably constitute from about 5% to about 15% by weight of an emulsionconcentrate, preferably, non-ionic surfactants are utilized.

The choice of concentration of the ester of formula I and the rate ofapplication to the insect infested area depends, of course, on severalfactors e.g., maturity of insects present, the type of insecticidalcomposition used and the method of application.

In order to illustrate our invention, the following examples are givenwherein the Chrysanthemum monocarboxylic acid chloride employed wasobtained from the corresponding commercial (i) Chrysanthemum carboxylicacid. In each case the particular carboxylic acid used consisted ofacis/trans mixture in the ratio of about 30:70%

EXAMPLE 1 Preparation of:5-methyl-5hexen-2-ynyl(i)-cis/trans-2,Z-dimethyl-3-(Z-methyl-propenyl)-cyclopropane carboxylate A solution of 14.0 g ofChrysanthemum monocarboxylic acid chloride in 50 ml of dry benzene wasadded dropwise at 20C in a nitrogen atmosphere over a period of 0.5 hourto a stirred solution of 9.07 g of 5-methyl-5-hexen-2-yn-l-ol and ll.85g of dry pyridine in ml of dry benzene. The resulting mixture wasstirred at 20C in a nitrogen atmosphere for 48 hours, then theprecipitated pyridine hydrochloride was filtered off and washed withbenzene. The combined filtrate and washings were washed successivelywith 5N aqueous hydrochloric acid, 2-N aqueous sodium hydroxidesolution, 2-N aqueous hydrochloric acid, saturated aqueous sodiumbicarbonate solution and brine, dried over anhydrous sodium sulphate,filtered and evaporated. Distillation yielded: 5-methyl-5-hexen-2- ynyl(i)-cis/trans-2,2-dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylate.

B.P. 128-129C/0.2 mm

EXAMPLE 2 Preparation of:6-methyl-5-hepten-2-ynyl(i)-cis/trans-2,2-dimethyl-3-(Z-methyl-propenyl)-cyclopropane carboxylate Using the proceduredescribed in Example 1. 6-methyl-5-hepten-2-yny](i)-cis/trans-2.Z-dimethyl- 3-(Z-methyI-propenyl)-cyclopropanecarboxylate was EXAMPLE 3 Preparation of: 5,6-dimethyl-5-hepten-2-yny1(i)-cis/trans-2,2-dimethy1-3-(Z-methyl-propenyl)- cyclopropanecarboxylate.

Using the procedure described in Example 1, the ester was prepared from5,6-dimethyl-5-hepten-2-ynl 01 and chrysanthemum monocarboxylic acidchloride.

EXAMPLE 4 Preparation of: cis'2,5-hexadienyl(i)-cis/trans-2,2-dimethyl-3-(2-methyl-propeny1)- cyclopropanecarboxylate.

Approximately 1 g of activated charcoal was added to a solution of 9.6 gof 5-hexen-2-yn-1-ol in 500 ml of petroleum ether (B.P. 60-80C) and theresulting mixture was warmed under a nitrogen atmosphere for one or twominutes, then immediately filtered. 2.5 g of LIN- DLAR catalyst(International Encyclopedia of Chemical Science, D. Van Nostrand Co.,Inc. 1964;690) was added to the filtrate with 20 ml of a 5% solution ofquinoline in petroleum ether. The resultant mixture obtained wasimmediately hydrogenated under atmospheric pressure at 20C untilthecalculated amount of hydrogen had been absorbed. The catalyst was thenfiltered off and the filtrate was evaporated. The residual syrup wasdissolved in 500 ml ofether and the solution obtained was washed with asaturated solution of so dium chloride in 2-N aqueous hydrochloric acidwith brine, dried over anhydrous sodium sulphate and anhydrous potassiumcarbonate, filtered and evaporated. Distillation yielded:cis2,5-hexadien-1-ol, (B.P. 68 69C/l5 mm; n 1.4615.)

A solution of 14 g of Chrysanthemum monocarboxylic acid chloride in 50ml of dry benzene was added dropwise over 0.5 hour at 20C under anitrogen atmosphere to a stirred solution of 8.1 g ofcis-2,5-hexadienl-ol and 11.85 g of dry pyridine in 120 ml of drybenzene. The resulting mixture was stirred at 20C for a further 23hours, then filtered. The filtrate was washed successively with diluteaqueous hydrochloric acid, 2-N aqueous sodium hydroxide solution, diluteaqueous hydrochloric acid, saturated aqueous sodium bicarbonate solutionand brine, dried over anhydrous sodium sulphate, filtered andevaporated. Distillation of the resid ual syrup yielded:cis-2,5-hexadienyl (i)-cis/trans-2,2-dimethy1-3-(Z-methyl-pfopenyl)-cyclopropane carboxylate.

B.P. 9590C/0.25mm n 1.4870

EXAMPLE Preparation of: trans-2,5-hexadienyl(i)cis/trans-2,2dimethyl-3-(2-methyl-propenyl)- cyclopropanecarboxylate.

4 g of lithium aluminium hydride was added to 400 ml of dry ether undera nitrogen atmosphere. A solution of 1 1.5 g of 5-hexen-2-yn-1-ol in 50ml ofdry ether was then added over a period of minutes, cooled and thenthe resulting mixture heated under reflux conditions for 7 hoursfollowed by cooling and slow treated successive additions of 7 ml ofwater and 60 ml of aqueous 2-N sodium hydroxide solution. Theprecipitate which formed was recovered and a trace of hydroquinoneadded. Distillation of the residue yielded: trans-2,5-hexadien-1-ol,B.P. 4245C/0.8 mm; n 1.4610.

Using the procedure described in Example 4, trans-2,5-hexadienyl(t)cis/trans-2,2-dimethyl-3-(2- methyl-propenyl)-cyclopropanecarboxylate was prepared from trans-2,5-hexadien-1-ol and Chrysanthemummonocarboxylic acid chloride. Distillation in the presence of a trace ofhydroquinone yielded trans-2,5- hexadienyl (i)cis/trans-2,2-dimethyl-3-(Z-methylpropenyl)-cyclopropane carboxylate.

B.P. C/1.0mm

EXAMPLE 6 Preparation of: 2-trans-2,.5-heptadienyl(i)-cis/trans-2,2-dimethyl-3-(2-methyl-propenyl)- cyclopropanecarboxylate.

Using the procedure described in Example 4, 2-trans 2,5-heptadienyl(i)-cis/trans-2,2-dimethyl-3- (Z-methyl-propenyl)-cyclopropanecarboxylate was prepared from 2-trans-2,5-heptadien- 1-01 andchrysanthemum monocarboxylic acid.

B.P. 142C/0.2mm

EXAMPLE 7 Preparation of: trans-S-methyl-Z,S-hexadienyl(i)-cis/trans-2,2-dimethyl-3-(2-methyl-propenyl)- cyclopropanecarboxylate.

Using the procedure described in Example 4,trans-5-methyl-2,5-hexadienyl (i)-cis/trans-2,2dimethyl-3-(2-methyl-propenyl)-cyclopropane carbox' ylate was preparedfrom trans-5-methyl2,S-hexadien- 1-01 and Chrysanthemum monocarboxylicacid chloride.

B.P.. 118120C/O.2mm

EXAMPLE 8 Preparation of: 2,5-hexadiynyl(i)-cis/trans-2,2-dimethyl-3-(2-methyl-propenyl)- cyclopropanecarboxylate.

Ethyl magnesium bromide was prepared from 24.2 g of magnesium and 109 gof ethyl bromide in ml of tetrahydrofuran. The resulting solution wasfiltered and diluted with 300 ml oftetrahydro-furan. 28.2 g of redis'tilled propargyl alcohol were added dropwise over 0.5 hour and theresulting mixture was then heated under reflux for 1.5 hours and thenallowed to cool. 1.5 g of cuprous chloride was added, followed by theaddition of a solution of 60 g-of redistilled propargyl bromide in 20 mlof tetrahydrofuran. The mixture obtained was heated under reflux for 16hours and the recovered product distilled rapidly in the presence ofhydroquinone under an atmosphere of nitrogen. Redistillation yielded:2,5-hexadiynyl-l-ol. B.P. 6870C/0.6mm; n 1.5015.

A solution of 14 g Chrysanthemum monocarboxylic acid chloride in 30 mlof dry benzene was added to a stirred solution of 7.8 g of2,5-hexadiyn-l-ol and 11.85 g of dry pyridine in 1 20 ml of dry benzene.The addition was made dropwise over a 30 minute period and under anitrogen atmosphere at 20C. The resulting mixture was stirred under thenitrogen atmosphere for a further period of 64 hours, then theprecipitated pyridine hydrochloride was filtered off and washed withbenzene. The combined filtrate was washed successively with diluteaqueous hydrochloric acid, 2-N aqueous sodium hydroxide solution, diluteaqueous hydrochloric acid, saturated aqueous sodium bicarbonate solutionand brine; and dried over sodium sulphate. Thereafter, several crystalsof hydroquinone were added. Distillation of the residue under nitrogenyielded: 2,5-hexadiynyl (i)-cis/trans-2,2-dimethyl-3-(Z-methyl-propenyl)-cyclopropane carboxylate.

B.P. 157 to 158C EXAMPLE 9 Preparation of: 4-phenyl-2-butynyl (i)cis/trans-2,2-dimethyl-3-(2-methyl-propenyl)- cyclopropane carboxylate.

A crystal of iodine was added to a suspension of 12.2 g of dry magnesiumin 120 ml of dry ether followed by the addition of 78.5 g ofbromo-benzene dropwise over a period of 45 minutes with stirring andcooling. The mixture was further stirred for minutes at 0 10C and theresulting GRIGNARD solution was separated from the unreacted magnesiumdry ether. A solution of 26.3 g of 4-chloro-2-butyn-1-ol in ml of dryether was then aded to the stirred GRlGNARD solution over a period of 20minutes at 20C, stirred at 20C for an additional 45 minutes and heatedunder gentle reflux for 80 minutes. After cooling the mixture was pouredinto a saturated aqueous ammonium chloride solution and ice solution andextracted three times with ether. Ether extracts were combined andwashed twice with brine, dried over anhydrous sodium sulphate, filteredand evaporated. Distillation of the residue yielded:4-phenyl-2-butyn-1-ol of boiling point 143150"C/15mm;-n,, 1.5581.

Using the latter procedure described in Example 8, 4-phenyl-2-butynyl(i)cis/trans-2,2-dimethyl-3-(2- methyl-propenyl)-cyclopropanecarboxylate was prepared from chrysanthemum monocarboxylic acid chlorideand 4-phenyl-2-butyn-l-ol.

B.P. 172 174C/0.65mm

EXAMPLE 10 Preparation of: 4-(Z-methyl-phenyl)-2-butynyl(i)-cis/trans-2,2-dimethyl-2-(2-methyl-propenyl)- cyclopropanecarboxylate.

Using the procedure described in Example 9, 4-(Z-methylphenyl)-2-butynyl(i)-cis/trans-2,2- dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylate was prepared from 4-(2-methylphenyl)-2-butynl-ol andchrysanthemum monocarboxylic acid chloride.

B.P. 190/200C/0.9mm

EXAMPLE 1 1 Preparation of: trans-4-phenyl-2-butenyl(i)-cis/trans-2,2-dimethyl-3-(2-methyl-propenyl)- cyclopropanecarboxylate.

Using the procedure described in Example 9, trans-4-phenyl-2-butenyl(i)-cis/trans-2,2-dimethyl-3- (2-methyl-propenyl)-cyclopropanecarboxylate, was prepared from trans-4-phenyl-2-buten-1ol andchrysanthemum monocarboxylic acid chloride.

12 B.P. 168l70C/1.4mm n 1.5200

EXAMPLE 12 9.5 g of the sodium salt of chrysanthemum monocarboxylic acidare ground to a fine powder and dissolved, with stirring, in 400 ml ofdiglyme at C under an atmosphere of nitrogen. 8.65 g ofl-bromo-S-methylhex-5-en-2-yne in 80 ml of diglyme are added dropwiseover a period of 0.25 hour with stirring The mixture is heated at C for88 hours under an atmosphere of nitrogen. The precipitated solids arefiltered off and the diglyme is removed under reduced pressure (5 mmHg). The residue is treated with water and extracted three times withether. The ether extracts are combined and washed twice with water,twice with 2-N sodium hydroxide solution and twice with sodium chloridesolution and then dried over anhydrous sodium sulfate. After filtrationand evaporation of the ether, the residue is distilled to yield5-methyl-5-hexen-2-ynyl (i)-cis/trans-2,2-dimethyl-3-(2-methylpropenyl)- cyclopropane carboxylate ofboiling point 145151C/ 1.0 mm (bath temperature C); n 1.4920.

EXAMPLE 13 7.2 g of the sodium salt of chrysanthemum monocarboxylic acidare finely powdered and suspended in 400 ml ofdiglyme. A solution of 6.3g of 1-chloro-4-phenyl- 2-butyne in 50 ml of diglyme is added and themixture is stirred and heated in an oil bath at 140C under a nitrogenatmosphere for 100 hours. The precipitated sodium chloride is filteredoff and the diglyme is removed under reduced pressure. The residue istreated with water and extracted three times with 150 ml of other eachtime. The ether extracts are combined, washed successively with 2-Nsodium hydroxide solution, water and sodium chloride solution and thendried over sodium sulfate. The solution is then filtered, evaporated andthe residue distilled. 5.1 g of a product of boiling range 112 150C/1.00.8 mm (bath temperature C) are obtained. Purification of this productby chromatography on aluminum oxide using petroleum ether (boiling range40 60C) as the eluant yielded 3.3 g of 4-phenyl-2-butynyl(i)-cis/trans-2,Z-dimethyl- 3-(2-methyl-propenyl)-cyclopropanecarboxylate; m, 1.5285.

EXAMPLE 14 2.5 g of 5-methyl-5-hexen-2-ynyl (i)-cis/trans-2,2-dimethyl-3-(2-methyl-propenyl)-cyclopropane carboxylate were dissolvedin sufficient kerosene to give a final volume of 100 ml. The resultingsolution was suitable for use as a spray.

Similar solutions were prepared in an analogous manner fromcis-2,5-hexadienyl (:t)-cis/trans-2,Z-dimethyl-3-(Z-methylpropenyl)-cyclopropane carboxylate, from 2,5-hexadiynyl(i)-cis/trans-2,2-dimethyl-3-(Z-methylpropenyl)-cyclopropane carboxylateand from 4-phenyl-2-butynyl'(i)-cis/trans-2,2-dimethyl-3-(Z-methylpropenyl)cyclopropanecarboxylate.

EXAMPLE 15 20 g of 5-methyl-5-hexen-2-ynyl (:)-cis/trans-2,2-dimethyl-3-(Z-methyl-propeny])-cyclopropane carboxylate, 10 g ofnonoxylon-lS (a non-ionic surfactant) and 70 g of xylene were thoroughlymixed to give a solution which could be used as an emulsifiableconcentrate.

Similar emulsifiable concentrates were prepared in an analogous mannerfrom cis-2,5-hexadienyl (i)-cis/trans-Z,2-dimethyl-3-(2-methyl-propenyl)- cyclopropane carboxylate,from 2,5-hexadiynyl (i) ci s/trans-2,2-dimethyl-3-(Z-methyl-propenyl)-cyclopropane carboxylate and from 4-phenyl'2-butynyl(i)-cis/trans-2,2-dimethyl-3(2-methylpropenyl)- cyclopropanecarboxylate.

Before use, the emulsifiable concentrates are emulsified in sufficientwater to give a ten-fold dilution.

EXAMPLE l6 EXAMPLE l7 15 g of -methyl-5-hexen-2-ynyl (i)-cis/trans-2,2-dimethyl-3-(Z-methyl-propenyl)-cyclopropane carboxylate were well mixedwith 80 g of a mixture of diatomaceous earth and kaolin and 5 g ligminsulphonate. The resulting mixture is crushed to the desired degree offineness to give a wettable powder which when dispersed in anappropriate amount of water can be applied by spraying.

Similar wettable powders were obtained in analogous manner fromcis-2,5-hexadienyl (i)-cis/trans-2,2-dimethyl-3-(2-methylpropenyl)-eyclopropane carboxylate, from2,5-hexadiynyl (i)-cis/trans-2,2-dimethyl-3-(Z-methyl-propenyl)-cyclopropane carboxylate and from4-phenyl2-butynyl (i)-cis/trans-2,2-dimethyl-3-(2-methyl-propenyl)-cyclopropane carboxylate.

EXAMPLE 18 2.5 g of 5-methyl-5-hexen-2-ynyl (t)-cis/trans-2,2-dimethyl-3-(2-methyl-propenyl)-cyclopropane carboxylate were dissolvedin 20 ml of acetone. 97.5 g of 300- mesh diatom aceous earth added tothe solution and the resulting mixture was thoroughly stirred in amortar. Acetone was then evaporated off to give a 2.5% dust formulation.

Similar dust formulations were obtained in analogous manner from cis-2,5-hexadienyl (i)-cis/trans-2,2-dimethyl-3-(Z-methylpropenyl)-cyclopropane carboxylate. from2,5-hexadiynyl (i)-cis/trans-2,Z-dimethyl-3'(2-methyl-propenyl)-cyclopropane carboxylate and from4-pl1enyl2'butynyl (i)-cis/trans-2,2-dimethyl-3-(2-methyl-propenyl)-cyclopropane carboxylate.

EXAMPLE l9 Field-bean seedlings each infested with approximately 50 100black bean aphids (Aphis fabae) are sprayed with acetone solutions ofthe acgive material. The plants are placed singly in tubes in water. 24and 48 hours after application the dead and surviving aphids are countedand the LD of the active material is calculated. This LD is expressed asIOgm ofthe con centration of the acetone solution in g/cm Results:

Active material flgm LDNI LPhenyl-Z-butynyl (itcis/trans-Z,2-dimethyl2-( Z-methyl-propenyl cyclopropane carboxylate trans-4-phenyl-2-butenyl(i)-cis/trans 2,2-dimethyl-2-( Z-methyl-propenyl cyclopropanecarboxylate 5.6 Dimethyl 5-hepten-2-ynyl (i)-cis/trans-2,2-d|methyl-3-(2-methylpropenyl)-cyclopropane carboxylate 2,5Hexadiynyl -3.6(:)-cis/trans-2,2-dimethyl3-(Z-methyl-propenyhcyclopropane carboxylateEXAMPLE 20 Petri dishes are sprayed with an acetone solution of theactive material. 2-3 hours after application, 10 house flies (Muscadomestica), 4 5 days old, are put into each dish. The flies are examined1,3 and 24 hours later to ascertain whether they are dead or paralysedand the LD of the active material is calculated. This LD is expressed aslog of the concentration of the acetone solution in g/cm Results:

Active material l gm 50 5,o-Dimethyl-S-hepten-Lynyl 4.()(t)-cis/trans2,2-dimethyl-3-( 2-methy|-propenyl)- cyclopropanecarboxylate trans S MethyI-LS-heXadienyI (i-cis/trans-Z,2-dimethyl-3-(Z-methybpropenyl cyclopropane carboxylate 6-Methyl'5-hepten-2-ynyl(i)-cis/trans-2.2 2,2-dimethyl-3-( Lmethyl-propenyl )-cyclopropanecarboxylate 2,5-Hexadiynyl (i)-cisltrans-2,2-dimethyl-3-(2-methyl-propenyl)- cyclopropane carboxylate 4-Phenyl-2-butynyl -5.3 or6.2* (i)-cisltrans-2,2dimethyl-3-( Z-meIhyI-propenyl cyclopropanecarboxylate 4-(Z-Methyl-phenyl)-2-butynyl (i)-cis/trans-2,2-dimethyl-3-(Z-methyl-propenyl cyclopropane carboxylate trans-4-Phenyl-2-butenyl(i)-cis/trans 2,2-dimethyl-3-( Z-methyLpropenyl cyclopropane carboxylate*Syncrgiscd by a l0:l proportion of pipcronyl butoxidc.

EXAMPLE 21 Bean leaf discs each with a two-day old infestation of 20 40spider mites (Tetrunychus urticae) are sprayed with an acetone solutionof the active material. Two days after application an assessment is madeof the dead spider mites on the discs and after 6 days an assessmentofthe dead spider mites and ofthe eggs killed. The LD of the activematerial is calculated. This LD is expressed as log of the concentrationof the acetone solution in g/cm". Results:

Active material gm 6-Methyl-5-hepten-2-ynyl(i)-cis/trans-2,2-dimethyl-3-( 2-methyl-propenyl cyclopropanecarboxylate 2,5-Hexadienyl 3 (i)-cis/trans-Z,2-dimcthyl-3-(Z-methyLpropenyl cyclopropane-carhoxylate 4-Phenyl-2-hutynyl 4.5*(iJ-cis/trans-Z,2-dimethyl-3-( 2-methyl propenyl cyclopropanecarboxylate Syncrgiscd by a proportion of pipcronyl butoxidc. Synergiscdby a lU:l proportion of bis-(2,3.3.3-tetrachloropr0pyl)-ethcr.

EXAMPLE 22 Active material 2m sn 5.6-Dimethyl-S-hepten-2-ynyl 3.0(i)-cis/trans-2.2-dimethyl-3-(Z-methyl-propenyl) cyclopmpane carboxylate2.5-Hcxatliynyl (:)-cis/trrms-2.Z-dimethyl-3-( Z-methyl-propenylcyclopropane carboxylate 4-Phenyl'2-butynyl(:l-cis/trans-Z.2-dimethyl-3-(2-methyl-propenyl)- cyclopropanecarboxylate 4-(Z-Methyl-phenylj-2-butynyl (i)-cis/trans2.2-dimethyl-3-(2-methyl-propenyl)-cyclopropane carboxylate trans4-Phenyl-2-butenyl (i)-cis/trans-2,2-dimethyl 3-(Z-methyl-propenyl)-cyclopropane carboxylate EXAMPLE 23 Groups of three potato leaf discs(diameter 24 mm) are sprayed on one side with an acetone solution of theactive material. Approximately 0.5 hour after application, 10 Coloradobeatle (Leptinotarsa decemlineara) larvae (L l 2) are put onto eachgroup of discs (distribution: 3, 3, 4) which, are then put into aplastic cage. Counts of the damaged larvae are made 24 and 48 hourslater, the treated leaf discs being replaced by untreated discs at thefirst count. The LD of the active material is calculated. This LD isexpressed as logm of the concentration of the acetone solution in g/cm".Results:

Active material g", sn

5.o-Dimethyl-S-hepten-Z-ynyl (i)-cis/trans 3.() 2.2-dimethyl-3-tZ-methyI-propenyl )cyclopropane carhoxylate.

-Continued Active material 310 LDMI 4-Phenyl-2-butynyl(i)-cis/trans-2,2-dimethyl-3-(2-methyl-propenyl)- cyclopropane carboxylate 4.5

*Syncrgiscd by a 10:] ratio of bis-(2.3.3.3-tctrachloropropyl)-cthcr.

We claim:

1. An insecticidal composition comprising as an active ingredientthereof an insecticidally effective amount of a chrysanthemic acid esterof the formula:

wherein R is hydrogen or lower alkyl; and a carrier.

2. The composition of claim-l wherein the chyrsanthemic acid ester is4-phenyl-2-butynyl (i)-cis/trans-2,2-dimethyl-3-(Z-methyl-propenyl)-cyclopropane carboxylate.

3. A method of combatting undesirable insects, selected from thegroupconsisting of Musca domestica, bean aphid, red spider mite, codling mothand colorado beetle, which method comprises applying to an area,infested with said insects, an insecticidally effective amount of achrysanthemic acid ester of the formula:

wherein R is hydrogen or lower alkyl.

1. AN INSECTICIDAL COMPOSITION COMPRISING AS AN ACTIVE INGREDIENTTHEREOF AN INSECTICIDALLY EFFECTIVE AMOUNT OF A CHRYSANTHEMIC ACID ESTEROF THE FORMULA:
 2. The composition of claim 1 wherein the chyrsanthemicacid ester is 4-phenyl-2-butynyl ( + or -)-cis/trans-2,2-dimethyl-3-(2-methyl-propenyl)-cyclopropane carboxylate.3. A method of combatting undesirable insects, selected from the groupconsisting of Musca domestica, bean aphid, red spider mite, codling mothand colorado beetle, which method comprises applying to an area,infested with said insects, an insecticidally effective amount of achrysanthemic acid ester of the formula: